CN104998659B - It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method - Google Patents
It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method Download PDFInfo
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Abstract
The present invention provide it is a kind of be used to being catalyzed furfural or furfuryl alcohol and reset catalyst of the Hydrogenation for cyclopentanol, the catalyst is loaded catalyst, including active component and carrier；Active component is selected from one or both of Pt, Pd, Ru, Rh, Cu or Ni；Carrier is oxide, the oxide selected from one or both of Co, Al, Mn or Ce；The quality of active component is the 0.5~8.0% of carrier quality.The catalyst can obtain the cyclopentanol of high yield using furfural or furfuryl alcohol as raw material under gentle aqueous phase hydroconversion condition, and yield is up to 80%.A kind of sustainable, inexpensive, gentle effective method is provided for the production of important fine chemicals cyclopentanol.
Description
Technical field：
The present invention relates to catalyst preparation field, is used to be catalyzed furfural more particularly, to one kind or furfuryl alcohol resets hydrogenation
The catalyst of cyclopentanol is prepared, specifically, be related to one kind resets Hydrogenation ring as raw material using furfural or furfuryl alcohol in aqueous phase system
Catalyst of amylalcohol and preparation method thereof, also have and reset side of the Hydrogenation for cyclopentanol using the catalyst furfural or furfuryl alcohol
Method.
Background technology：
Cyclopentanol is a kind of important fine-chemical intermediate, is the raw material of medicine, dyestuff and perfume industry, and medicine
With the solvent of spices, industrially mainly for the preparation of bromocyclopentane, chlorocyclopentane and methyl ring amyl ether etc..At present, ring penta
The industrial process of ketone is mainly the adipic acid decarboxylation cyclisation method and cyclopentene oxidizing of petroleum path.Using adipic acid as raw material
Cyclopentanone is made through high temperature decarboxylation, cyclopentanol is then obtained by hydrogenation reaction, the technology path raw material relies on the life of adipic acid
Production, is related to multiple cumbersome reactions steps, and is related to decarboxylation procedure in production process, and Theoretical Mass yield is less than 60%, atom
Economy is not high, while produces substantial amounts of pollutant in process of production, and this preparation method is restricted increasingly.In addition, with
Cyclopentene made from the C 5 fraction processing of naphtha pyrolysis ethylene by-product is raw material, and ring can also be produced by hydration reaction
Amylalcohol, but due to needing to use the concentrated sulfuric acid in preparation process, high is required to the corrosion resistance of equipment, and concentrated sulfuric acid recovery is difficult,
Environmental pollution is very serious.Have that reaction conversion ratio is relatively low in direct hydration technique simultaneously, the internal circulating load of raw material cyclopentene compared with
Greatly.
With the increasingly depleted of fossil resource, using the catalyzed conversion of renewable resource, using increasingly causing, people's is extensive
Pay attention to.Furfural is derived from a kind of bulk chemical of agricultural wastes, be industrially with cheap corncob, bagasse,
The agriculture and forestry organic waste materials such as cotton seed hulls are raw material production.China is furfural production big country and big export country, Chinese furfural year in 2013
Yield accounts for more than the 80% of worldwide production total amount up to more than 30 ten thousand tons.Therefore, the exploitation of furfural downstream product has with added value lifting
There is considerable prospect, while its effective utilize can not only reduce dependence of the important chemical to petroleum resources, and
The added value of agricultural product can be increased.At present, furfural can prepare furfuryl alcohol, tetrahydrofurfuryl alcohol, 2- methyl furans by selective hydrogenation
Mutter, the chemicals such as 2- methyltetrahydrofurans, pentadiene, pentanediol.Furfuryl alcohol is wherein prepared as main utilization ways using furfural, accounted for
80% or so.Because furfural or furfuryl alcohol and cyclopentanone are respectively provided with five carbon atoms, therefore furfural or furfuryl alcohol are converted into ring
Pentanone or cyclopentanol cause everybody concern.
The content of the invention：
It is an object of the invention to provide a kind of catalyst for being catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation cyclopentanol, the catalysis
Agent is catalyzed furfural in the aqueous phase system of organic solvent-free or furfuryl alcohol resets hydrogenation reaction, catalytic activity gentle with reaction condition
High, the characteristics of cyclopentanol yield is high.
The catalyst of the present invention is loaded catalyst, including active component and carrier；The active component be selected from Pt,
One or both of Pd, Ru, Rh, Cu or Ni, preferably one or both of Ru, Pd, Cu, there is provided hydrogenation activity position；It is described
Carrier is selected from the oxidation of one or both of Co, Al, Mn or Ce oxide, preferably one or both of Co, Al or Mn
Thing, there is provided dehydration, rearranged active position；The mass fraction that the quality of active component accounts for carrier quality is 0.5~6.0%, preferably 1.0
~4.0%.
The preparation method of the catalyst is：First pass through coprecipitation and prepare carrier, then by equi-volume impregnating or
The catalyst is prepared in excessive infusion process, specifically includes following steps：
(1) it is 1 by alcohol-water quality ratio:1~1:5 (preferably 1:1~1:3) it is made into mixed solvent；By cobalt acetate, aluminum nitrate,
One or both of manganese nitrate or cerous nitrate add the in the mixed solvent, are completely dissolved to obtain salting liquid, the concentration of solution
For 0.1~0.6mol/L；
(2) aqueous sodium carbonate, wherein CO are prepared3 2-Ion concentration is 0.3-0.9mol/L, and satisfaction can precipitate institute completely
State the metal cation in salting liquid；
(3) single droplet method or double drop methods are used, the aqueous sodium carbonate of the salting liquid of step (1) and step (2) is total to
Precipitation, stirred when being added dropwise, as the precipitation in mixed solution gradually increases, until the pH value in mixed solution reaches 8~10,
It can stop；Mixed solution after co-precipitation carries out aging, then through filtering, washing, dry (preferably 120 DEG C), then in Muffle
12-24h (preferably 500 DEG C) is calcined in stove, obtains oxide.
(4) for the oxide obtained using step (3) as carrier, load active component obtains the catalyst.
Further, the concrete operations of above-mentioned steps (4) are：By ruthenic chloride, chloroplatinic acid, palladium nitrate, copper nitrate, nickel nitrate
Or one or both of rhodium nitrate is soluble in water obtains solution, using equi-volume impregnating or excessive infusion process, it is added to
In above-mentioned carrier, the quality for meeting active component is the 0.5~8.0% of carrier quality；After impregnating (preferably 24h), done in air
Dry (preferably 120 DEG C), then place and 12-24h (preferably 500 DEG C) is calcined in Muffle furnace, the catalyst can be obtained after cooling.
Further, the preferred methanol of above-mentioned alcohol, ethanol, ethylene glycol or glycerine.The preferred cobalt acetate of solute, aluminum nitrate or nitre
One or both of sour manganese.
Further, in step (4), solute is one or both of ruthenic chloride, palladium nitrate or copper nitrate, meets activity
The quality of component is the 1.0~4.0% of carrier quality.
It is without any organic solvent that the catalyst furfural or furfuryl alcohol of the present invention, which resets Hydrogenation for the reaction of cyclopentanol,
Aqueous phase reactions, the preparation method comprises the following steps：First, the catalyst of preparation is added into reaction under high pressure after hydrogen reducing
In kettle, furfural or furfuryl alcohol are added, adds deionized water, is well mixed, seals autoclave；Wherein, the matter of furfural or furfuryl alcohol
Amount is 2~20% (preferably 5~15%) of deionized water quality；The quality of catalyst is the 1~20% of furfural or furfuryl alcohol quality
(preferably 5~10%)；Then, with the air (repeatedly replaceable, to reach more preferable effect) in nitrogen displacement autoclave,
The nitrogen (can be multiple, to reach more preferable effect) in autoclave is replaced with hydrogen again, afterwards in 2~6MPa hydrogen pressure
Under (preferable Hydrogen Vapor Pressure is 3~5MPa)；2~10h is reacted at 100~200 DEG C, and (preferable reaction temperature is 120~160
DEG C, the reaction time be 4~8h).
The invention provides a kind of catalyst for being catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation cyclopentanol and use the catalyst
Method, by resetting hydrogenation catalyst, high conversion generates cyclopentanol with high selectivity.The catalyst of the present invention is adapted to pure water phase
Hydrogenation reaction, organic solvent-free use, and reaction process is simple, mild condition, and whole course of reaction is substantially without coking carbon distribution.In temperature
Under the conditions of the aqueous phase of sum, higher conversion ratio and cyclopentanol yield can be reached in 10h, compared with prior art, reaction effect
Rate significantly improves.The preparation method technique of the catalyst of the present invention is simple in addition, and easy to operate, catalyst, which can be repeated several times, to be made
With and activity significantly reduces.
Brief description of the drawings：
The above-mentioned and/or additional aspect and advantage of the present invention will become from the following description of the accompanying drawings of embodiments
Substantially and it is readily appreciated that, wherein：
Fig. 1 is the GC-MS spectrograms for the product that the embodiment of the present invention 5 is reset Hydrogenation cyclopentanol by furfuryl alcohol.
Fig. 2 is the GC spectrograms for the product that the embodiment of the present invention 16 is reset Hydrogenation cyclopentanol by furfural.
Fig. 3 is cobalt aluminum oxide supported ruthenium catalyst (Ru/CoAlO made from the embodiment of the present invention 6x) XRD.
Fig. 4 is Mn oxide supported ruthenium catalyst (Ru/MnO made from the embodiment of the present invention 18x) XRD.
Embodiment：
The present invention is described in more detail below by instantiation, the embodiment provided is given for example only the present invention, but
It is not in any way limit the scope of the present invention.
Embodiment 1
Catalyst preparation：(1) it is 1 by methanol-water mass ratio:1 is made into mixed solvent, aluminum nitrate, cobalt acetate is added mixed
In bonding solvent, it is completely dissolved to form salting liquid (being referred to as solution A), aluminum nitrate, the concentration of cobalt acetate are respectively 0.2mol/L；
(2) with aqueous sodium carbonate (being referred to as solution B), concentration 0.6mol/L；(3) solution B is gradually slowly added into solution A
In, it is stirring while adding, as the precipitation in solution gradually increases, when the pH value in mixed solution reaches 8~10, you can stop
Only.Then, the solution containing precipitation is subjected to aging 12h, most afterwards through filtering, wash, 120 DEG C of dry 24h, then in Muffle furnace
After 500 DEG C of calcining 24h, aluminium cobalt/cobalt oxide (AlCoOx) is obtained；(4) with obtained aluminium cobalt/cobalt oxide (AlCoOx) for carrier, etc.
Volume impregnation chlorination ruthenium solution prepares load Ru catalyst, and Ru content of metal is 4.0wt.%, is obtained after drying, roasting
4.0Ru/AlCoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：4.0Ru/AlCoOx catalyst prepared by the above method is added into autoclave after hydrogen reducing
In, add furfural, deionized water is well mixed, sealing autoclave；Wherein, the quality of furfural is deionized water quality
2%；The quality of catalyst is the 5% of furfural quality；Then, it is multiple with the air in nitrogen displacement autoclave, then use hydrogen
Nitrogen in gas displacement autoclave is multiple, is filled with 2.0MPa hydrogen afterwards, and 2h is reacted at 100 DEG C, and reaction is completed cold
But to room temperature, liquid phase component is analyzed with gas-chromatography and GC-MS, reaction evaluating condition and the results are shown in Table 1.
Embodiment 2
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for alcohol-water mass ratio as 1:2, its
Remaining operating procedure in the same manner as in Example 1, is finally made 4.0Ru/AlCoOx loaded catalysts and is used for furfural/furfuryl alcohol aqueous phase rearrangement
The reaction of Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 2.
Embodiment 3
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:3,
Aqueous sodium carbonate (being referred to as solution B) concentration is adjusted to 0.3mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
Obtain 4.0Ru/AlCoOx loaded catalysts and be used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 3.
Embodiment 4
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for glycerol-water mass ratio as 1:2,
Aqueous sodium carbonate (being referred to as solution B) concentration is adjusted to 0.9mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
Obtain 4.0Ru/AlCoOx loaded catalysts and be used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 4.
Embodiment 5
Catalyst preparation：(1) it is 1 by ethylene glycol-water quality ratio:5 are made into mixed solvent, and aluminum nitrate, cobalt acetate are added
In the mixed solvent, it is completely dissolved to form salting liquid (being referred to as solution A), aluminum nitrate, the concentration of cobalt acetate are respectively 0.3mol/L；
(2) with aqueous sodium carbonate (being referred to as solution B), concentration 0.6mol/L；(3) solution B is gradually slowly added into solution A
In, it is stirring while adding, as the precipitation in solution gradually increases, when the pH value in mixed solution reaches 8~10, you can stop
Only.Then, the solution containing precipitation is subjected to aging 6h, most afterwards through filtering, wash, 120 DEG C of dry 24h, then in Muffle furnace
After 500 DEG C of calcining 12h, aluminium cobalt/cobalt oxide (AlCoOx) is obtained；(4) with obtained aluminium cobalt/cobalt oxide (AlCoOx) for carrier, etc.
Volume impregnation chlorination ruthenium solution prepares load Ru catalyst, and Ru content of metal is 4.0wt.%, is obtained after drying, roasting
4.0Ru/AlCoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 5.
Embodiment 6
Catalyst preparation：(1) it is 1 by ethylene glycol-water quality ratio:2 are made into mixed solvent, and aluminum nitrate, cobalt acetate are added
In the mixed solvent, it is completely dissolved to form salting liquid (being referred to as solution A), aluminum nitrate, the concentration of cobalt acetate are respectively 0.1mol/L；
(2) with aqueous sodium carbonate (being referred to as solution B), concentration 0.6mol/L；(3) solution B is gradually slowly added into solution A
In, it is stirring while adding, as the precipitation in solution gradually increases, when the pH value in mixed solution reaches 8~10, you can stop
Only.Then, the solution containing precipitation is subjected to aging 12h, most afterwards through filtering, wash, 120 DEG C of dry 12h, then in Muffle furnace
After 500 DEG C of calcining 12h, aluminium cobalt/cobalt oxide (AlCoOx) is obtained；(4) with obtained aluminium cobalt/cobalt oxide (AlCoOx) for carrier, etc.
Volume impregnation chlorination ruthenium solution prepares load Ru catalyst, and Ru content of metal is 4.0wt.%, is obtained after drying, roasting
4.0Ru/AlCoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 6.
Embodiment 7
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Remaining operating procedure in the same manner as in Example 1, is finally made 4.0Ru/AlCoOx loaded catalysts and is used for furfural/furfuryl alcohol aqueous phase weight
Arrange the reaction of Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 7.
Embodiment 8
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for platinum acid chloride solution, and in the same manner as in Example 1,4.0Pt/AlCoOx loads are finally made in remaining operating procedure
Type catalyst is used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 8.
Embodiment 9
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for palladium nitrate solution, and in the same manner as in Example 1,4.0Pd/AlCoOx loads are finally made in remaining operating procedure
Type catalyst is used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 9.
Embodiment 10
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for rhodium nitrate solution, and in the same manner as in Example 1,2.0Rh/AlCoOx loads are finally made in remaining operating procedure
Type catalyst is used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 10.
Embodiment 11
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for copper nitrate solution, and in the same manner as in Example 1,8.0Cu/AlCoOx loads are finally made in remaining operating procedure
Type catalyst is used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 11.
Embodiment 12
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for nickel nitrate solution, and in the same manner as in Example 1,8.0Ni/AlCoOx loads are finally made in remaining operating procedure
Type catalyst is used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 12.
Embodiment 13
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for the mixed solution of ruthenic chloride and palladium nitrate, and remaining operating procedure in the same manner as in Example 1, is finally made
2.0Ru2.0Pd/AlCoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 13.
Embodiment 14
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Chlorination ruthenium solution is substituted for the mixed solution of ruthenic chloride and copper nitrate, and remaining operating procedure in the same manner as in Example 1, is finally made
2.0Ru2.0Cu/AlCoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 14.
Embodiment 15
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Remaining operating procedure in the same manner as in Example 1, is finally made 0.5Ru/AlCoOx loaded catalysts and is used for furfural/furfuryl alcohol aqueous phase weight
Arrange the reaction of Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 15.
Embodiment 16
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Remaining operating procedure in the same manner as in Example 1, is finally made 4.0Ru/AlCoOx loaded catalysts and is used for furfural/furfuryl alcohol aqueous phase weight
Arrange the reaction of Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 16.
Embodiment 17
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Remaining operating procedure in the same manner as in Example 1, is finally made 6.0Ru/AlCoOx loaded catalysts and is used for furfural/furfuryl alcohol aqueous phase weight
Arrange the reaction of Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 17.
Embodiment 18
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Add manganese nitrate and form solution A, manganese nitrate concentration is 0.1mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
4.0Ru/MnOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 18.
Embodiment 19
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Add cerous nitrate and form solution A, nitric acid cerium concentration is 0.6mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
4.0Ru/CeOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 19.
Embodiment 20
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Add cobalt acetate and form solution A, acetic acid cobalt concentration is 0.4mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
4.0Ru/CoOx loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 20.
Embodiment 21
Catalyst preparation：It is 1 the methanol-water mass ratio in embodiment 1:1 is substituted for ethylene glycol-water quality ratio as 1:2,
Add aluminium acetate and form solution A, acetic acid aluminum concentration is 0.4mol/L, and remaining operating procedure in the same manner as in Example 1, is finally made
4.0Ru/Al2O3 loaded catalysts are used for the reaction that furfural/furfuryl alcohol aqueous phase resets Hydrogenation cyclopentanol.
Reaction evaluating：The operation sequence of reaction evaluating is consistent with embodiment 1, but its reaction condition and the results are shown in Table in 1
Implement shown in 21.
Comparative example 22
This comparative example catalyst is Raney CuNi (the general Chemical Co., Ltd. in Dalian), the operation sequence of reaction evaluating with
Embodiment 1 is consistent, but its reaction condition and the results are shown in Table shown in implementation 22 in 1.As a result show, compared with embodiment 16,
The Ru catalyst of AlCoOx loads has higher catalytic efficiency than Raney CuNi catalyst, can be reached in the short period higher
Conversion ratio and selectivity, reaction can reach within 4 hours 76% cyclopentanol yield, and Raney CuNi catalyst reactions 20 hours
Afterwards,
Cyclopentanol yield just only has 48%.
The condition and reaction result of the catalyst reaction evaluation of 1 each embodiment of table
Claims (2)
1. catalyst resets Hydrogenation for the application process in cyclopentanol in catalysis furfural or furfuryl alcohol, it is characterised in that
The application process is：The catalyst is added in autoclave after hydrogen reducing, furfural or furfuryl alcohol is added, adds
Enter deionized water, be well mixed, seal autoclave；Wherein, the quality of furfural or furfuryl alcohol be deionized water quality 5~
20%, the quality of catalyst is the 10% of furfural or furfuryl alcohol quality；Then, with the air in nitrogen displacement autoclave, then
With hydrogen displacement autoclave in nitrogen, afterwards 2~6MPa hydrogen depress, at 100~200 DEG C react 2~
10h；
The catalyst is loaded catalyst, including active component and carrier；The active component is Ru；The carrier is aluminium
Cobalt/cobalt oxide；The quality of active component is the 4.0% of carrier quality；The catalyst is prepared by following steps：
(1) it is 1 by alcohol-water quality ratio:1~1:5 are made into mixed solvent；Solute is added into the in the mixed solvent, is completely dissolved
Salting liquid is obtained, the concentration of solution is 0.1~0.6mol/L；Solute is cobalt acetate and aluminum nitrate；The alcohol is selected from methanol, second
Alcohol, ethylene glycol or glycerine；
(2) aqueous sodium carbonate, wherein CO are prepared3 2-Ion concentration is 0.3-0.9mol/L；
(3) single droplet method or double drop methods are used, the aqueous sodium carbonate of the salting liquid of step (1) and step (2) is co-precipitated,
Until the pH value in mixed solution reaches 8~10；Mixed solution after co-precipitation carries out aging 6-12h, then through filtering, washing
Wash, dry, then 12-24h is calcined in Muffle furnace, obtain oxide；
(4) oxide obtained using step (3) is carrier；Solution is obtained by ruthenic chloride is soluble in water, using equi-volume impregnating
Or excessive infusion process, it is added in the carrier, the quality for meeting active component is the 4.0% of carrier quality；It is empty after dipping
Dried in gas, then place in Muffle furnace and calcine 12-24h, the catalyst can be obtained after cooling.
2. application process as claimed in claim 1, it is characterised in that the quality of furfural or furfuryl alcohol is the 5 of deionized water quality
~15%, the hydrogen pressure of reaction is 3~5MPa, and reaction temperature is 120~160 DEG C, and the reaction time is 4~8h.
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